Insecticidal sulfonates

ABSTRACT

Substituted aryl alkane sulfonates having insecticidal properties.

United States Patent [191 Partos [4 1 Sept. 16, 1975 Related US.Application Data [62] Division of Ser. No, 17,902, March 9, 1970, Pat.No.

[52] US. Cl. 424/303 [51] Int. Cl. A0lN 9/14 [58] Field of Search424/303 r [56] References Cited UNITED STATES PATENTS 2,485,095 10/1949Harris et a1. 424/303 3,179,684 4/1965 Covey et a1 424/303 FOREIGNPATENTS OR APPLICATIONS 951,741 3/1964 United Kingdom Primary ExaminerV.D. Turner Attorney, Agent, or Firm-Richard H. Shear ABSIRACT Substitutedaryl alkane sulfonates having insecticidal properties.

16 Claims, No Drawings INSECTICIDAL SULFONATES This is a division ofapplication Ser. No. 17,902, filed Mar. 9, 1970, now U.S. Pat. No.3,818,102.

This invention relates to new and useful aryl alkane sulfonates and theinsecticidal compositions containing at least one of them. The compoundsof this invention can be represented by the formula wherein m and n areintegers from through 4 with a maximum sum of 4; R is alkyl, haloalkyl,having from 1 through 1 8 carbon atoms, alkenyl or haloalkenyl havingfrom 2 through 18 carbon atoms, aralkyl having from 7 through 1 1 carbonatoms; R, R and R are by drogen, alkyl, alkoxy or thioalkyl having fromI through 6 carbon atoms, R50 cyano, nitro, trifiuoromethyl, carboxy,acetyl, acetoxy or carboxamine with a maximum of 2 of R, R and R beinghydrogen. When two of the ring substituents are hydrogen, and the otheris alkyl, the total number of carbon atoms in the ring substituents isin excess of 2.

The alkyl substituents in these compounds can be methyl, ethyl, normalpropyl, isopropyl, normal butyl, secondary butyl, tertiary butyl, normalpentyl, isopenty], and the various forms of hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl. hexadecyl,heptadecyl, and octadecyl.

The compounds of the present invention can be readily prepared by thereaction of an appropriate substituted phenol with an alkaneorhaloalkane sulfonylchloride in the presence of an acid acceptor such asan amine. The preparation of these compounds is illustrated by thefollowing examples.

EXAMPLE 1 About 50 grams of 3-methyl-4-cyanophenol was introduced into asuitable reaction vessel provided with means for agitation. The phenolwas dissolved in 100 ml. of diethyl ether and about 38 grams oftriethylamine. To this solution was added approximately 43 grams ofmethanesulfonylchloride and the reaction mixture was stirred forapproximately 3 hours. The reaction mixture was then washed with waterand the organic layer separated. After drying over magnesium sulfate,filtering, and evaporation, the residue solidified upon cooling and wasrecrystallized from carbon tetrachloride to obtain a solid having amelting point of 75-78C. The product, 4-cyano-3-methylphenylmethanesulfonate, was analyzed with the following results: Calcd. for CH NO S. Theory 51.17%C, 4,2971-H. Found 51.13%C, 4.23%H.

EXAMPLE 2 About 7.3 grams of 3-hydroxybenzotrifluoride was introducedinto a suitable reaction vessel having means for agitation. The compoundwas then dissolved in approximately 150 ml. of diethyl ether. About 5.7grams of methanesulfonyl chloride and about 5.0 grams of triethylaminewere then added and stirred for 12 hours at which time the reaction wassubstantially complete. The reaction mixture was washed with water andwith ether, dried and condensed to obtain an oil which solidified oncooling to provide a solid having a melting point of 30-32C. Theproduct, 3-trif1uoromethylphenyl methanesulfonate, gave the followinganalysis: Calcd for: C H F O S Theory 40.0%C, 2.94%H. Found 40.36%C,3.09%1-1.

Other compounds of the present invention that can be prepared insubstantially the same manner using properly substituted reactantsinclude: 4-nitrophenyl methanesulfonate 2,4-dinitrophenylmethanesulfonate 3-isopropyl-4-nitrophenyl methanesulfonate3-isopropyl-4cyanophenyl methanesulfonate 3,4,5-trimethylphenylmethanesulfonate 3-isopropylphenyl methanesulfonate 3,4-diethylphenylmethanesulfonate 3methyl-4-nitrophenyl methanesulfonate 3-nitrophenylmethanesulfonate 4-cyanophenyl methanesulfonate 3-methyl-4-cyanophenylmethanesulfonate 3-cyano-4,6-dinitrophenyl methanesulfonate3,5-dicyanophenyl methanesulfonate 3-trifluoromethylphenylmethanesulfonate 3-trifluoromethylphenyl trifluoromethanesulfonate3-n-propyl-4-cyanophenyl-n-propanesulfonate 3-isopropyl-4-n-propylphenylisopropanesulfonate 3-isopropyl-4-cyanophenyl-t-butanesulfonate3,4,5-triethylphenyl methanesulfonate 3,4,5-trichloromethylphenylsecondary butanesulfonate 2-methyl-4-cyano-S-isopropylphenylmethanesulfonate 2-isopropyl-4-cyano-5-methylphenyl methanesulfonate2-cyano-5-isopropylphenyl methanesulfonate 2-cyano-4-isopropylphenylmethanesulfonate 3,5-dimethyl-4-cyanophenyl methanesulfonateZ-isopropyl-4-cyanophenyl methanesulfonate 3-t-butyl-4-cyanophenylmethanesulfonate 3-isopentyl-4-cyanophenyl methanesulfonate3-isopropyl-4-acetylphenyl methanesulfonate 3-isopropyl-4-carboxyphenylmethanesulfonate 3-isopropyl-4-acetoxyphenyl methanesulfonate3-isopropyl-4-carboxamidephenyl methanesulfonate2-acetyl-5-isopropylphenyl methanesulfonate 2-carboxy-5-isopropylphenylmethanesulfonate 2-acetoxy-5-isopropylphenyl methanesulfonate2-carboxamide-5-isopropylphenyl methanesulfonate3-isopropyl-4-cyanophenyl decanesulfonate 3-isopropyl-4-cyanophenylhexadecanesulfonate 3-isopropyl-4-cyanophenyl octadecanesulfonate3-isopropyl-4-cyanophenyl benzylsulfonate 3-isopropyl-4-cyanophenylchlorobenzylsulfonate 3-isopropyl-4-cyanophenyl methoxybenzylsulfonate3-isopropyl4-cyanophenyl nitrobenzylsulfonate The terms insect" andinsecticide are used herein in their broad common usage to includespiders, mites, ticks, and like pests which are not in the strictbiological sense classed as insects. Thus, the term insect" is used torefer not only to those small invertebrate animals belonging mostly tothe class lnsecta, comprising six-legged, usually winged forms, asbeetles, bugs, bees, flies, and so forth, but also to other alliedclasses of arthropods whose members are Wingless and usually have morethan six legs, as spiders, mites, ticks, centipedes, millipedes. andwood lice.

In order to demonstrate the utility of the compound of this inventionagainst corn root worm larvae, aryl alkyl sulfonates of this inventionwere incorporated into soil containing corn root segments and the soilwas infested with western corn root worm larvae. The soil was thenmaintained for 48 hours at 25C. and the larval mortality determined. A100% mortality rate was obtained with soil containing 6 ppm of3isopropyl'4- cyanophenyl methanesulfonate. In repetitions of thisprocedure, 100% larval mortality rates were also obtained when3,4,5-trimethylphenyl methanesulfonate and 3-isopropyl-4-cyanophenylethanesulfonate were used as the active component.

The compounds under consideration are also effective against the bollweevil and the bollworm. For example, when 3-isopropyl-4-cyanophenylmethanesulfonate was sprayed on cotton plants at the rate of 10 lbs. peracre, a 100% kill of boll weevil was obtained and a 60% kill ofbollworm.

The utility of the compounds of this invention to destroy cattle ticks(Boophilus microplus), which are parasitic to domestic animals ingeneral, and to cattle in particular, is illustrated by the followingprocedure. In this procedure, 3-isopropyl-4-cyanophenyl methanesulfonatewas dissolved in a trichloroethylene-olive oil mixture and impregnatedin chromatagraphic paper. The triehloroethylene is permitted toevaporate, leaving only olive oil and the sulfonate on the paper. Theunfed larval ticks (Boophilus microplus) were exposed to the compound bycontact with the treated surfaces.

The 3-isopropyl-4-cyanophenyl methanesulfonate was added to the mixtureto provide a solution or suspension in which the concentration of thecompound in the olive oil was 1.12% (i.e., 1.12 grams of compound in 100ml. of olive oil). Portions of this stock solution were then diluted toprovide solutions of 0.07, 0.035, 0.017, 0.008, 0.004, 0.002 and 0.001percents respectively.

The chromatographic paper was cut into rectangles of 9 cm. by 7.5 cm.Each of the rectangular papers was then supported horizontally by fourpins and a 0.67 ml. portion of the sulfonate solution was run on to eachof the papers. The papers were then dried, evaporating thetrichloroethylene, thus leaving the olive oil with the active ingredientimpregnated in the paper. The papers were then formed into packets witha clip. This left one end open. One hundred larvae were introduced intoeach packet and the opening closed with a clip. After 48 hours at roomtemperature, the packets were opened and the number of larvae alive anddead were counted.

In accordance with this procedure, a strain of cattle ticks susceptibleto known acaricides and a strain of cattle ticks resistant to them wereexposed to the 3-isopropyl-4-cyanophenyl methanesulfonate. The procedurewas also conducted using a commercially availphosphorothioate. Theresults obtained, expressed as percentage kill of the larvae, are setforth below.

In actual practice, the sulfonates are usually formulated into a cattledip in which the cattle to be protected are immersed. Such dips areprepared by dissolving the sulfonates, with or without other pesticides,in a water-immiscible solvent system and a sufficient quantity of one ormore emulsifying agents is added to insure the formation of a stableaqueous emulsion. Water is then added to the emulsifiable concentrate toform an emulsion containing from about 0.0l% to about 1.0% of the activeingredients.

A typical cattle dip concentrate in accordance with this invention hasthe following approximate composi' tion by weight:

3-isopropyl-4-cyanophenyl methanesulfonate 10% Sodium dodecylbcnzenesulfonate 571 Polyoxyethylene sorbitan condensate 10% High-boilingaromatic petroleum fraction 25% Cyclohexanone 5071 When added to waterat the rate of one gallon of concentrate to about 100 gallons of water,a stable emulsion containing about 0.1% by weight of the sulfonate isobtained. It has been found that cattle infested with cattle ticks andimmersed in, or sprayed with, such an acaricide are completely devoid ofticks within a relatively short period of time.

Although the compounds of this invention are useful per se incontrolling a wide variety of insect pests, it is preferable that theybe supplied to the pests or to the environment of the pests in adispersed form in a suitable extending agent.

The term dispersed is used herein in its widest possible sense.Particles of the compounds may be molecular in size and held in truesolution in a suitable organic solvent, or the particles may becolloidal in size and distributed throughout a liquid phase in the formof suspensions or emulsions, or in the form of particles held insuspension by wetting agents. The term includes particles which aredistributed in a semi-solid viscous carrier such as petrolatum or soapor other ointment base in which they may be actually dissolved in thesemisolid or held in suspension in the semi-solid with the aid ofsuitable wetting or emulsifying agents. The term dispersed also meansthat the particles may be mixed with and distributed throughout a solidcarrier providing a mixture in particulate form, eg pellets, granules,powders, or dusts. The term dispersed also includes mixtures which aresuitable for use as aerosols including solutions, suspensions, oremulsions of the compounds of this invention in a carrier such asdichlorodifluoromethane and the like which boil below room temperatureat atmospheric pressure.

The expression extending agent as used herein includes insecticidaladjuvants and any and all of the subable acaricide,O,O'diethy1'3,56trichloroz'pyrldyl stances in which the compounds ofthis invention are Acaricide Ticks Concentration Sulfonatc SusceptibleI00 I00 I00 100 100 100 of this invention Resistant l00 I00 100 I00 I000 0 Commer- Susceptible I00 100 100 I4 0 0 0 ciul Product Resistant I000 0 O 0 0 0 dispersed. It includes, therefore, the solvents of a truesolution, the liquid phase of suspensions, emulsions or aerosols, thesemi-solid carrier of ointments and the solid phase of particulatesolids, e.g. pellets, granules, dusts and powders.

The exact concentration of the compounds of this in' vention employed incombatting or controlling insect pests can vary considerably providedthe required dosage (i.e., toxic or lethal amount) thereof is suppliedto the pests or to the environment of the pests. When the extendingagent is a liquid or mixture of liquids (e.g., as in solutions,suspensions, emulsions, or aerosols) the concentration of the activecompound employed to supply the desired dosage generally will be in therange of 0.0001 to 50% by weight. When the extending agent is asemi-solid or solid, the concentration of the insecticide employed tosupply the desired dosage generally will be in the range of 0.1 to 75%by weight. From a practical point of view, the manufacturer must supplythe user with a concentrate in i such form that, by merely mixing withwater or solid extender (e.g. powdered clay or talc) or other low-costmaterial available to the user at the point of use, he will have aneasily prepared insecticidal spray or particulate solid. In such aconcentrate composition, the insecticide generally will be present in aconcentration of 5 to 95% by weight, the residue being any one or moreof the wellknown insecticidal adjuvants, such as the various surfaceactive agents (e.g. detergents, a soap or other emulsifying or wettingagents), surface-active clays, solvents, diluents, carrier media,adhesives, spreading agents, humcctants, and the like.

There are a large number of organic liquids which can be used alone orin combination for the preparation of solutions, suspensions oremulsions of the phosphonatcs of this invention. For example, isopropylether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbontetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptaneand like higher liquid alkanes, hydrogenated naphthalene, solventnaphtha, benzene, toluene, xylene, petroleum fractions (e.g. thoseboiling almost entirely under 400F. at atmospheric pressure and having aflash point above about 80F, particularly kerosene), mineral oils havingan unsulfonatable residue above about 80% and preferably above about90%. In those instances wherein there may be concern about thephytotoxicity of the organic liquid extending agent a portion thereofcan be replaced by such low molecular weight aliphatic hydrocarbons asdipentene, diisobutylene, propylene trimer, and the like or suitablepolar organic liquids such as the aliphatic ethers and the aliphaticketones containing not more than about l0 carbon atoms as exemplified byacetone, methyl ethyl ketone, diisobutyl kctone, dioxane, isopropylether, and the like.

The insecticides of this invention are preferably supplied to the insectpests or to the environment of the insect pests in the form of emulsionsor suspensions. Emulsions or suspensions are prepared by dispersing thecompounds either per se or in the form of an organic solution thereof inwater with the aid ofa watersoluble surfactant. The term surfactant" asemployed herein is used as in volume ll of Schwartz, Perry and Eerchs"Surface Active Agents and Detergents I958, lntcrscience PublishersInc., New York) in place of the expression emulsifying agent to connotcgenerically the various emulsifying agent, "dispersing agents, wettingagents and spreading agents that are adapted to be admixed with theactive compounds of this invention in order to secure better wetting andspreading of the active ingredients in the water vehicle or carrier inwhich they are insoluble through lowering the surface tension of thewater (see also Frear Chemistry of Insecticides, Fungicides andHerbicides", second edition, page 280). These surfactants include thewell-known capillary-active substances which may be anionic, cationic,or non-ionic which are described in detail in volumes I and II ofSchwartz, Perry and Berchs Surface Active Agents and Detergents 1958,Interscience Publishers, Inc., New York) and also in the November, 1947issue of Chemical Industries (pages 811-824) in an article entitledSynthetic Detergents by John W. McCutcheon and also in the July, August,September and October 1952 issues of Soapand Sanitary Chemicals underthe title Synthetic Detergents. The disclosures of these articles withrespect to surfactants are incorporated in this specification byreference in order to avoid unnecessary enlargement of thisspecification. The preferred surfactants are the water-soluble anionicnonionic surface-active agents set forth in US. Pat. No. 2,846,398(issued Aug. 5, 1958). In general, a mixture of watersoluble anionic andwater-soluble non-ionic surfactants is preferred.

The compounds of this invention can be dispersed by suitable methods(e.g. tumbling or grinding) in solid extending agents either of organicor inorganic nature and supplied to the insect pests environment inparticulate form. Such solid materials include for example, tricalciumphosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite,attapulgite, fullers earth, pyrophillite, diatomaceous earth, calcinedmagnesia, volcanic ash, sulfur and the like inorganic -solid materialsas well as organic materials such as powdered cork, corn husks, corncobs, powdered wood, and powdered walnut shells. The preferred solidcarriers are the adsorbent clays, e.g. bentonite. These mixtures can beused for insecticidal purposes in the dry form, or by addition ofwater-soluble surfactants or wetting agents the dry particulate solidscan be rendered wettable by water so as to obtain stable aqueousdispersions or suspensions suitable for use as sprays.

For special purposes the compounds of this invention can be dispersed ina semi-solid extending agent such as petroleum or soap (.e.g sodiumstearate or oleate or palmitate or mixtures thereof) with or without theaid of solubility promoters and/or surfactants or dispersing agents.

In all of the forms described above, the dispersions can be providedready for use in combatting insect pests or they can be provided inconcentrated form suitable for mixing with or dispersing in otherextending agents. As illustrative of a particularly useful concentrateis an intimate mixture of a compound of this invention with awater-soluble surfactant in the weight proportions of 0.1 to l5 parts ofsurfactant with sufficient sulfonate to make I00 parts by weight. Suchas concentrate is particularly adapted to be made into a spray forcombatting various forms of insect pests by the addition of waterthereto.

Another useful concentrate adapted to be made into a spray forcombatting a variety of insect pests is a solution (preferably asconcentrated as possible) of a compound of this invention in an organicsolvent therefor.

The saidv liquid concentrate preferably contains dissolved thereinaminor amount (e.g. 0.5 to 10% by weight of the weight of the newinsecticidal agent) of a water-soluble surfactant (or emulsifyingagent).

Of the surfactants aforementioned in preparing the various emulsifiable,wettable or dispersible compositions or concentrates of thisinvention,'the anionic and non-ionic surfactantsare preferred. Of theanionic surfactants, the particularly preferred are the well knownwater-soluble alkali metal alkyl-aryl sulfonates as exemplified bysodium decylbenzene sulforiate and sodium dodecylbenzenesulfonate. Ofthe non-ionic surfactants, the particularly preferred are thewatersoluble polyoxyethylene derivatives of alkylphenols (particularlyisooctylphenol) and the water-soluble polyoxyethylene derivatives of themono-higher fatty acid esters of hexitol anhydrides (e.g. sorbitan).These materials in general contain to moles of ethylene oxide per moleof the hexitol anhydride or the alkylphenol.

The compositions of this invention can also contain other additamentssuch as fertilizers and pesticides used as, or in combination with, thecarrier materials. For example, the insecticides useful in combinationwith the above described compounds include parathion, methyl parathion,pyrethrine, nicotine, aldrin, chlordane, heptachlor, toxaphene,malathion, 2- isopropoxyphenyl N-methylcarbamate, 0,0,0,0- tetramethyl0,0'-thiodi-p-phenylene phosphorothioate, dimethyl phosphate ofcrotonamide, fenthion, carbofuran, mirex, DDT, dicofol, methoxychlor,dichlorvos, demeton, dimethoate, carbophenothion, ronnel, carbaryl,azinphosmethyl, methomyl, aldicarb and the like.

In controlling or combatting insect pests the compounds of thisinvention either per se or compositions containing them are supplied tothe insect pests or to their environment in a lethal or toxic amount.This can be done by dispersing the new insecticidal agent orinsecticidal composition comprising same in, on or over an infestedenvironment or in, on, or over an environment the insect pests frequent,e.gv agricultural soil or other growth media or other media infestedwith insect pests or attractable to the pests for habitational orsustenance or propagational purposes, in any conventional fashion whichpermits contact between the insect pests and the compounds of thisinvention. Such dispersing can be brought about by applying sprays, dipsor particulate solid compositions to a surface infested with the insectpests or attractable to the pests as for example, animals such as sheepand cattle, the surface of an agricultural soil or other media such asthe above ground surface of plants by any of the conventional methods,e.gl power dusters, boom and hand Sprayers, and spray dusters. Also forsub-surface application such dispersing can be carried out by simplymixing the new insecticidal agent per se or insecticidal spray ofparticulate 3-hydroxy-N-methyl-cissolid compositions comprising samewith the infested environment or with. the environment'the insect pestsfrequent,'or by employing a liquid carrier for the new insecticidalagent to accomplish subsurface penetration and impregnation therein.

While this invention has been described with respect to certainembodiments, his to be understood that it is not so limited and thatvariations and modifications thereof obvious to those skilled in the artcan be made without departing from the spirit and scope thereof.

What is claimed is:

i 1. An insecticidal composition comprising a carrier and aninsecticidally effective amount of 2,4- dinitrophenyl methane sulfonate.

2. An' insecticidal composition comprising a carrier and aninsecticidally effective amount of 3- isopropylphenyl methanesulfonate.

3. An insecticidal composition comprising a carrier and aninsecticidally effective amount of 3,45- trimethylphenylmethanesulfonate.

4. An insecticidal composition comprising a carrier and aninsecticidally effective amount of 3-isopropyl-4- nitrophenylmethanesulfonate.

5. A method of combattinginsects which comprises contacting said insectswith a toxic amount of 2,4- dinitrophenyl methanesulfonate.

6. A method of combatting insects which comprises contacting saidinsects with a toxic amount of 3- isopropylphenyl methanesulfonate.

7. A method of combatting insects which comprises contacting saidinsects with a toxic amount of 3,4,5- trimethylphenyl methanesulfonate.

8. A method of combatting insects which comprises contacting saidinsects with a toxic amount of 3-isopropyl-4-nitrophenylmethanesulfonate.

9. A method of combatting soil-borne insects which comprises introducinginto the soil a toxic amount of 2,4-dinitrophenyl methanesulfonate.

10. A method in accordance with claim 9 wherein said insects are comrootworms.

l 1. A method of combatting soil-borne insects which comprisesintroducing into the soil a toxic amount of 3-isopropylphenylmethanesulfonate.

12. A method in accordance with claim 11 wherein said insects are comrootworms.

13. A method of combatting soil-borne insects which comprisesintroducing into the soil a toxic amount of 3,4,5-trimethylphenylmethanesulfonate.

14. A method in accordance with claim 13 wherein said insects are comrootworms.

15. A method of combatting soil-borne insects which comprisesintroducing into the soil a toxic amount of 3-isopropyl-4-nitrophenylmethanesulfonate. I

16. A method in accordance with claim 15 wherein saidinsects are cornrootworms.

1. AN INSECTICIDAL COMPOSITION COMPRISING A CARRIER AND ANINSECTICIDALLY EFFECTIVE AMOUNT OF 2,4-DINITROPHENYL METHANE SULFONATE.2. An insecticidal composition comprising a carrier and aninsecticidally effective amount of 3-isopropylphenyl methanesulfonate.3. An insecticidal composition comprising a carrier and aninsecticidally effective amount of 3,4,5-trimethylphenylmethanesulfonate.
 4. An insecticidal composition comprising a carrierand an insecticidally effective amount of 3-isopropyl-4-nitrophenylmethanesulfonate.
 5. A method of combatting insects which comprisescontacting said insects with a toxic amount of 2,4-dinitrophenylmethanesulfonate.
 6. A method of combatting insects which comprisescontacting said insects with a toxic amount of 3-isopropylphenylmethanesulfonate.
 7. A method of combatting insects which comprisescontacting said insects with a toxic amount of 3,4,5-trimethylphenylmethanesulfonate.
 8. A method of combatting insects which comprisescontacting said insects with a toxic amount of 3-isopropyl-4-nitrophenylmethanesulfonate.
 9. A method of combatting soil-borne insects whichcomprises introducing into the soil a toxic amount of 2,4-dinitrophenylmethanesulfonate.
 10. A method in accordance with claim 9 wherein saidinsects are corn rootworms.
 11. A method of combatting soil-borneinsects which comprises introducing into the soil a toxic amount of3-isopropylphenyl methanesulfonate.
 12. A method in accordance withclaim 11 wherein said insects are corn rootworms.
 13. A method ofcombatting soil-borne insects which comprises introducing into the soila toxic amount of 3,4,5-trimethylphenyl methanesulfonate.
 14. A methodin accordance with claim 13 wherein said insects are corn rootworms. 15.A method of combatting soil-borne insects which comprises introducinginto the soil a toxic amount of 3-isopropyl-4-nitrophenylmethanesulfonate.
 16. A method in accordance with claim 15 wherein saidinsects are corn rootworms.